Triazinyl carboxy-alkyl sulphides and salts thereof



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Patented Mar. 2, 1943 I PATENT OFFICE 'mmznwr. CARBOXY-ALKYL SULPHIDES" YAND SALTS THEREOF Gaetano F. D Alclio and James W. Underwood, Pittsfield, Mass., assignors to General Electric Company, a corporation of New York "To Drawing. Application becember 4, 1941,

, ,\SerialNo.421,682

Claims.

This invention relates to new chemical compounds and more particularly to triazine derivatives. The invention especially is concerned with I the production of new and useful trlazinyl carboiw-alkyl sulphides and salts thereof.

The chemical compounds of this invention may be represented by the following general formula:

In the above formula 11. represents an integer is at least 1 and not more than 2, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halo-hydrocarbon radicals, and Z represents aOmember of the class consisting of hydrogen and elements and radicals that can be substituted for the hydrogen atom of a COOH grouping, more particularly the alkali metals (sodium, potassium, lithium, caesium and rubidium) and e ammonium (-NH4) radical. Thus, when I stands for hydrogen the triazinyl carboxy-alkyl sulphides of this invention may be represented by the formula where n and R have the meanings above given.

with reference to Formula I. When Z in For:- mula I is other than hydrogen, the compounds of the invention may be represented by the forcooM grouping, specifically an alkali-metal or the ammonium radical, and n and R have the meanings above given with reference to Formula I.

will be seen that, since 11, represents an integer which is for 2, the linkage of the secondary butyl, isobutyl, butenyl, amyl, meth- -allyl, tertiary butyl, crotyl,.ethal1yl, .heptyl, iso- 15 heptyboctyl, decyl, isoamyl, hexyl, etc.) including cycloaliphatic (e. g., .cyclopentyl, cyclopenteriyl, cyclohexyl, 'cyclohexenyl, cycloheptyl, eta); aryl '(e. g., phenyl, diphenyl or xenyl, "naphthyl, etc.) ;-aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allyl enyl, Z-butenylphenyl, tertiarybutylphenyl, letcJ; aryl-substituted aliphatic te.-g., benzyl, 'phenylethyl, phenylisopropyl, cinnamyl, etc.) and their homologues, as well as those groups with one or more of theirhydrogen atoms substituted by, for example, a halogen. Specific examples of halogeno-substituted hydrocarbon -radicals are chloromethyl, chloroethyl, chlorophenyl, dichlqrophenyl, chlorocyclohexyl, ethyl'chlorophenyl, phenylchloroethyl, bromo-v ethyL'bmmopropyi bromotolyl, etc. Preferably R in Formulas I, II and III is hydrogen. Howeventhere also may be produced in accordance with the present invention chemical compounds such, for instance, as those represented by the general formulas:

NHR

4 IV N/ \N I BEN- zJ-sc,.n,,. ooon and, more particularly, 5 NHR v I I I BEN-k c-s-cmcoon 1/ 3 N where w. and R have the samemeanin'gs as above given with reference jto Formula I.

The new compounds of thi invention may be From a-consideration of the above formulas it used as chemotherapeutic agents andas inter- Illustrative examples of radicals that R in the mediates in the preparation of derivatives thereof such as ureido, hydrazine, acyl, carbamyl, amidine, etc., derivatives of the individual-compound embraced by Formula. I. Compounds containing a COOH grouping may be esterified or amidated; or the hydrogen of the carboxyl grouping may be replaced by a substituent such, for instance, as an ammonium radical or a monovalent metal, e. g., an alkali metal such as sodium, potassium, lithium, etc., thereby to obtain compounds such as represented by Formula III. These new chemical compounds also may be compounded with rubber, both natural and synthetic, to modify the properties of the rubber.

The organic sulphides of the present invention, especially those containing a COOH grouping, are particularly valuable in the preparation of synthetic resinous compositions. Thus they may be condensed with, for instance, aldehydes, including polymeric aldehydes and aldehyde-addition products, to yield condensation products of particular utility in the plastics and coating arts. Our new compounds containing a COOH grouping are especially useful when intercondensed with amidogen-aldehyde (e. g., ureaformaldeh yde, melamine-formaldehyde, etc.) partial condensation products to effect or to accelerate the conversion of such partial condensation products from a soluble, fusible state to a cured or insoluble and infusible state. Condensation products of these new organic sulphides with aldehydes are more fully described and claimed in our copending application Serial No. 431,540, filed February 19, 1942, and assigned to the same assignee as the present invention.

Various methods may be employed to produce the chemical compounds of this invention. We prefer to prepare them by eiiecting reaction, in' the presence of a hydrohalide acceptor, between a diamino [(--NHR) 2] mercapto symmetrical triazine (s-triazine) and a halo alkyl monobasic acid or a water-soluble salt of such an acid, e. g., an ammonium salt oran alkali-metal salt. We prefer to use analkali-metal salt, for instance the sodium or potassium salt, of a halo-alkyl monobasic acid.. When a 'salt of the acid is used, there is first produced a salt (for example, an ammonium oran alkali-metal salt depending upon the particular starting reactant) of the diamino s-triazinyl carboxy-alkyl sulphide. The carboxy derivative is obtained by treating this salt with hydrochloric, hydrobromic, sulphuric or other suitable organic or inorganic acid in an amount just sufiicient to decompose the salt and to convert the COOM grouping of'the triazine derivd ative to 2. COOH grouping.

Illustrative examples of mercapto diammo striazines that may be used, depending upon the particular end-product desired, are:

z-mercapto 4,6-diamino s-triazine (i-mercapto 2,6-diamino s-triazine; G-mercapto 2,4-diamino) s-triazine z-mercapto 4,6-di-(methylamino) s-triazine z-mercapto 4,6-di-(anilino) s-triazine Z-mercapto 4-amino G-ethylamino s-triazine '2-mercapto 4,6-di-(propylamino) s-triazine z-mercapto d-allylamino G-butylamino s-triazine -2-mercapto 4-isobutylamino fi-cyclopentylamino 2 mercapto 4 cycloheptylamino fi-isopropylphenylamino s-triazine Z-mercapto 4-isopropylanilino 6-phenylpropylamino s-triazine 2-mercapto e-dichloroanilino fi-chloroethylamino I s-triazine 2-mercapto- 4-amino S-bromoethylamino s-triazine 2-mercapto 4-amino 6-methylamino s-triazine 2-mercapto 4-amino 6-benzylamino s-triazine 2-mercapto 44-n-hexylamino 6-xenylamino s-trizine Z-mercapto 4-cycl0hexenylamino G-naphthyla- Illustrative examples of halo-alkyl monobasic acids and water-soluble salts of halo-alkyl monobasic acids that may be employed, depending upon the particular end-product desired, are

chloroacetic acid Bromoacetic acid Iodoacetic acid Alpha-chloropropionic acid Beta-chloropropionic acid Alpha-bromopropionic acid Beta-bromopropionic acid Alpha-iodopropionic acid Beta-iodopropionic acid Alpha-chlorobutyricacid Alpha-chloro isobutyric acid Beta-chlorobutyric acid Beta-chloro isobutyric acid Alpha-bromo isobutyric acid Phenyl chloroacetic acid Alpha-chloro pentanoic acid dium hydroxide, potassium hydroxide, etc.

Beta-chloro pentanoic acid Beta-iodo pentanoic acid Alpha-tolyl beta-phenyl beta-chlorobutyric acid Alpha-benzyl alpha-cyclopentyl beta, beta-dinaphthyl beta iodo propionic acid Alpha-naphthyl beta-chlorophenyl beta-bromo butyric acid and the alkali-metal and ammonium salts of halo-alkyl monobasic acids such as above mentionedby way of illustration, for example the sodium, potassium, lithium, etc., salts of such halo-alkyl monobasic acids.

Various hydrohalide acceptors may -be employed. We prefer to use a hydrohalide acceptor that will react with the mercapto triazine to form a water-soluble salt. Examples of such acceptors are the alkali-metal hydroxides, e. g., 50-

ditional examples of hydrohalide acceptors that may be used are other inorganic bases, e. g., calcium hydroxide, vbarium hydroxide, ammonium hydroxide, etc.; carbonates of inorganic bases, in-

cluding the carbonates of alkali metals; organic amines such as tertiary amines, e. g., trimethyl amine, triethyl amine, tributyl amine, pyridine, dimethyl aniline, quinoline, etc.; quaternary ammonium bases, e. g., tetramethyl ammonium hydroxide, etc.; and the like.

The reaction between the mercapto diamino s-triazine and the halo-alkyl monobasic acid (or water-soluble salt thereof) may be carried out in any suitable manner, but preferably is effected in the presence of a suitable solvent or mixture of solvents. Although various solvents and solvent mixtures may be employed, for economic reasons and because of their eminent suitability we prefer to use water or a mixture of water and alcohol. The reaction may be carried out under a variety of temperature and pressure conditions, for instance at normal or at elevated temperatures and at atmospheric, sub-atmospheric or super-atmospheric pressures.

When the starting reactant is a halo-alkyl monobasic acid, the reaction may be represented by the following general equation:

represents the salt of the acid represented'by HA.

The new chemical compounds of this invention also may be prepared by effecting reaction NHR C N N X(C,.Rr..) C 00131 hydrohalide acceptor n RHN-C C- S H NHR N N II I +salt of hydrohalide RHN-C c-scnmn coon acceptor N In the above equation X represents halogen,

and n and R have the same meanings as given\ above with reference to Formula I.

When a water-soluble salt, specifically an ammonium salt or an alkali-metal salt, of a haloalkyl monobasic acid is used as a starting reactbetween a halogenated diamino s-t'riazine (that is, a diamino s-triazine having a halogen atom attached directly to a carbon atom of the triazine nucleus) and a mercapto-alkyl monobasic acid (or a suitable salt thereof), e. g., the alkali-metal salt thereof in the presence of a hydrohalide acceptor. This reaction may be carried out by any suitable means but preferably is effected in the presence of-an anhydrous solvent, e. g., alcohol. The other conditions of reaction may be the same as described above with reference to the firstmentioned method of preparation.

Inorder that those skilled in the art better may understand how the present invention may be carried into effect, the following illustrative examples are given. All parts are by weight.

Example 1 This example illustrates the preparation of diamino s-triazinyl carboxy-methyl sulphide.

- Parts Thioammeline 143.0 Sodium chloroacetate 116.5

Sodium hydroxide 40.0 Water 500.0

The stated amounts of thioammeline and sodim um hydroxide were dissolved in the stated ant in the preparation of a diamino s-triazinyl carboxy-alkyl sulphide, the following equations illustrate the reaction:

In the above equations (VII-A and VII-B) He. represents an acid capable of converting the CQOM grouping of the compound treated to a COOH grouping, specifically an inorganic acid g'., hydrochloric, hydrobromic, sulphuric, etc.) n and R have the meanings given above with reference to Formula I, and M has the meaning given above with reference to Formula III. MA

amount of water. The sodium chloroacetate "was now added and the resulting mixture was heated under reflux at the boiling temperature I Example 2 4,6-di-(methylamino) s-triazinyl-2 carboxymethyl sulphide, which also may be named 2,6- di-(methylamino) s-triazinyl-4 carboxy-methyl sulphide or 2,4-di-(methylamino) s-triazinyl-6 .carboxy-methyl sulphide, is prepared in essentially the same manner as described under Example 1 with the exception that 171 parts of Z-mercapto 4,6-di-(methylamino) s-triazine is used instead of 143 parts thioammeline.

Example 3 Diamino s-triazinyl alpha-(carboxy-ethyl) sulphide is prepared in essentially the same manner as described under Example 1 with the exception that 130.5 parts of the sodium salt of alphachloropropionic acid (sodium alphaechloropropionate) is employed instead of 116.5 parts of sodium chloroacetate:

' Example 4 Diamirro s-triazinyl beta-(carboxy-ethyD' sulphide is prepared in essentially the same manner as described under Example 1 with the exception that 130.5 parts of the sodium salt of beta-chloropropionic acid (sodium beta-chloropropionate) is used instead of 116.5 parts of sodium chloroacetate.

Other examples of the chemical compounds of this invention are listed below:

4-amino G-methylamino s-triazinyl-2 carboxymethyl sulphide 4,6-di- (ethylamino) s-triazinyl-2 carboxy-methyl sulphide 4,6-di-(anilino) sulphide 4,6-di- (chloroanilino) methyl sulphide 4,6-di-(cyclohexylamino) s-triazinyl-2 carboxymethyl sulphide 4,6-di-(anilino) s-triazinyl-Z alpha-(carboxyethyl) sulphide 4,6-di- (methylamino) s-triazinyl-2 alphacarboxy-propyl) sulphide 4-benzylamino 6-phenethylamino s-triazinyl-2 alpha-(alpha-phenyl beta-tolyl carboxy-ethyl) sulphide Y 4-cyclopentylamino 6-xy'lidino s-triazinyl-2 beta- (alpha, alpha-dibutyl beta-benzyl carboxypropyl) sulphide 4-anilino 6-methylamino s-triazinyl-2 carboxymethyl sulphide 4,6-diamino s-triazinyl-2 beta-(alpha-cyclohexyl carboxy-butyl) sulphide 1 4-amino G-naphthylamino s-triazinyl-Z ,carboxymethyl sulphide 4,6-di-(naphthylamino) s-triazinyl-2 (carboxy-ethyl) sulphide 4,6-diamino s-triazinyl-Z alpha-(carboXy-propyi) sulphide 4,6-diamino s-triazinyl-2 beta-(carboxy-propyl) sulphide 4,6-diamino s-triazinyl-2 alpha-(carboxy-butyl) sulphide s-triazinyl-2 carboxy-methyl s-triazinyl-2 carboxy- 4,6-diamino s-triazinyl-2 beta-(carboiry -butyl) sulphide 4,6-diamino s-triazinyl-Z alpha- (carboxy-pentyl) sulphide 4,6-diamino s-triazinyl-2' beta-(carboxy-pentyl) sulphide 4,6-diamino s-triazinyl-2 alpha-(carboxy-hexyl) sulphide 4,6-diamino s-triazinyl-2 beta-(carboxy-hexyl) sulphide 4,6-diamino s-triazinyl-2 beta-(alpha-chlorophenyl carboxy-butyl) sulphide 4,6-diamino s-triazinyl-2 carboxy-(chlorophenyl)-methyl sulphide 4-methylamino 6-toluido s-triazinyl-2 beta-(carboxy-ethyl) sulphide and the ammonium and alkali-metal (e. g., sodium, potassium, etc.) salts of the above-mentioned sulphides.

In a manner similar to that described above with particular reference to the diamino [(NHR) z] s-triazinyl carboxy-methyl and carboxy-ethyl sulphides, corresponding derivatives of the asymmetrical and vicinal triazines may be prepared. It also will be understood by those skilled in the art from the foregoing description of the preparation of a triazine monosulphide that similar compounds may be prepared in which two or three sulphur atoms are attached directly to a carbon atom of the triazine nucleus and which have attached to each sulphur atom a --(CnR2n)COOZ grouping, where n, R and Z have the meanings above given with reference to Formula I.

alpha- What we claim as new and desire to secure by Letters Patent of the United States is:

1. Chemical compounds corresponding to th general formula HR N arm-(1 where n is an integer and is at least 1 and not more than 2, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

4. Chemical compounds as in claim 3 wherein R represents hydrogen.

5. Chemical compounds corresponding to the general formula where n is an integer and is at least 1 and not more than 2, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

6. Diamino s-triazinyl carbon-methyl sulphide.

7. A diamino s-triazinyi carboxy-ethyl sul- Y phide.

8. Diamino s-triazinyl alpha-(carboxy-ethyl) sulphide.

9. Diamino s-triazinyl beta-(carboxy-ethyl) sulphide.

10. The method of preparing chemical compounds corresponding to thegeneral formula where n is an integer and is at least 1 and not between a mercapto triazine corresponding to the eneral formula i 'na c i i RHN-C c-sn I where R. has the meaning above given, and (2) a compound corresponding to the general formula X(CnR2n) 0002 where n is an integer and is at least 1 and not more than 2, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and M represents a member of the class consisting of the ammonium radical and alkali metals; said acid being employed in an amount just sumcient to convert the COOM grouping of the said co pound to a COOH grouping.

13. The method of preparing diamino s-triazinyl carboxy-methyl sulphide which comprises effecting reacticn,-in the presence of a hydrohalide acceptor, between thioammeline and an alkali-metal salt of chloroacetic acid thereby to; obtain the alkali-metal salt of diamino 's-triazinyl carboxy-methyl sulphide, and treating the I said alkali-metal salt with an inorganic 'acidfin an amount just sufiicient to convertit to diamino s-triazinyl carboxy-methyl sulphide.

14. A method as in claim 13 wherein the hydrohalide acceptor is an alkali-metal hydroxide.

15.,The method of preparing diamino s-triazinyl carboxy-methyl' sulphide which comprises effecting reaction, in the presence of sodium hydroxide, "between thioammeline and sodium chloroacetate thereby to obtain the sodium salt of diamino s-triazinyl carboxy-methyl sulphide, and treating the said sodium salt with hydrochloric acid in an amount just sufficient to form diamino s-triazinyl carboxy-methyl sulphide.

GAETANO F. DALELIO. JAMES w. UNDERWOOD. 

